CN115785407A - Method for preparing high-performance high-valued copolyester - Google Patents
Method for preparing high-performance high-valued copolyester Download PDFInfo
- Publication number
- CN115785407A CN115785407A CN202211525032.4A CN202211525032A CN115785407A CN 115785407 A CN115785407 A CN 115785407A CN 202211525032 A CN202211525032 A CN 202211525032A CN 115785407 A CN115785407 A CN 115785407A
- Authority
- CN
- China
- Prior art keywords
- polyester
- raw material
- acid
- polyester polyol
- copolyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000002994 raw material Substances 0.000 claims abstract description 112
- 229920000728 polyester Polymers 0.000 claims abstract description 92
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 68
- 230000035484 reaction time Effects 0.000 claims abstract description 31
- 238000002844 melting Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims description 47
- -1 ester compound Chemical class 0.000 claims description 39
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 24
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 24
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- 239000001361 adipic acid Substances 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 14
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 12
- 238000006068 polycondensation reaction Methods 0.000 claims description 12
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 9
- 230000032050 esterification Effects 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 14
- 235000011037 adipic acid Nutrition 0.000 description 12
- 239000002699 waste material Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229920005862 polyol Polymers 0.000 description 8
- 150000003077 polyols Chemical class 0.000 description 8
- WOZVHXUHUFLZGK-UHFFFAOYSA-N terephthalic acid dimethyl ester Natural products COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 239000001384 succinic acid Substances 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000009264 composting Methods 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 102100037458 Dephospho-CoA kinase Human genes 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 108010049285 dephospho-CoA kinase Proteins 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 239000003415 peat Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- VYZKQGGPNIFCLD-UHFFFAOYSA-N 3,3-dimethylhexane-2,2-diol Chemical compound CCCC(C)(C)C(C)(O)O VYZKQGGPNIFCLD-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- UVHLUYZMNUCVJN-UHFFFAOYSA-N 3-methyloctane-4,4-diol Chemical compound CCCCC(O)(O)C(C)CC UVHLUYZMNUCVJN-UHFFFAOYSA-N 0.000 description 1
- LYQWYIYZAKISGW-UHFFFAOYSA-N 3-oxabicyclo[3.2.2]nonane-2,4-dione Chemical compound O=C1OC(=O)C2CCC1CC2 LYQWYIYZAKISGW-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
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- 229920000877 Melamine resin Polymers 0.000 description 1
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
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- 229920000647 polyepoxide Polymers 0.000 description 1
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- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a method for preparing high-performance high-valued copolyester, which comprises the following steps: polyester polyol and polyester raw materials are mixed and react for 0.5 to 12 hours at the temperature of 190 to 280 ℃ under the stirring condition to complete the melting and depolymerization of the polyester raw materials, the mixture is continuously stirred and vacuumized, the temperature is controlled to be 180 to 300 ℃, the vacuum degree is controlled to be 1 to 500Pa, the reaction time is 0.5 to 12 hours, and the high-performance high-valued copolyester is obtained through polymerization. The invention upgrades the general polyester raw material into high-performance high-valued copolyester, and is particularly suitable for the field of preparing high-performance high-valued recycled polyester from recycled polyester.
Description
Technical Field
The invention relates to the technical field of copolyester preparation, in particular to a method for preparing high-performance high-valued copolyester.
Background
Polyester is an important polymer material, and has good mechanical properties, thermal stability, chemical corrosion resistance, repeatable processing and other properties, so that the polyester is widely applied to the fields of fibers, packaging materials, engineering plastics and the like. The enormous downstream demand has driven the mass production of polyesters. According to the raw material division, the polyester can be divided into two categories of copolyester and homopolyester, and the synthesis method of the copolyester comprises a chemical polymerization method and an enzyme polymerization method. The chemical polymerization method is the most widely used production method in industry, mainly comprising direct esterification polycondensation method and ester exchange polycondensation method, the main process is to react carboxylic acid, anhydride or carboxylic ester with excessive alcohol under the action of catalyst to obtain esterified substance, then to vacuumize under the action of catalyst to carry out polycondensation reaction to obtain high molecular weight copolyester. The direct raw materials of the two methods are both small molecules and are limited by factors such as the boiling point, side reaction, and reactivity of the small molecule raw materials, especially the boiling point, side reaction, and reactivity of the small molecule alcohol, and the side reaction, and reactivity of the small molecule acid, etc., and the esterification polycondensation method and the ester exchange polycondensation method generally require a high-efficiency catalyst or a long reaction time, thereby increasing the time cost, energy consumption, and the amount of byproducts. For example, polybutylene adipate terephthalate (PBAT) is produced by a direct esterification method using 1, 4-Butanediol (BDO), adipic Acid (AA), and terephthalic acid (PTA) as raw materials, or by a transesterification method using 1, 4-Butanediol (BDO), adipic Acid (AA), and terephthalic acid (DMT) as raw materials. The direct esterification method of adopting DMT ester exchange method to replace PTA can solve the problem of poor reaction activity of PTA, but flammable, explosive and toxic methanol can be generated in the reaction process, and the two process methods need to add high-efficiency catalysts in each step to shorten the reaction time; in the reaction process, BDO can be etherified to form a large amount of Tetrahydrofuran (THF) as a byproduct, about 1 ton of PBAT can be generated while 0.12 ton of THF is generated, a large amount of waste gas is generated while raw materials are wasted, and subsequent operations such as byproduct recovery, purification and the like are required; meanwhile, the color of the product is easy to yellow as the reaction time is prolonged. The production process of PBAT with large production capacity, low consumption and less three wastes is a problem to be solved urgently by the technical personnel in the field.
In particular, the method for preparing high-performance high-valued copolyester is particularly suitable for the field of preparing high-performance high-valued recycled polyester from recycled polyester.
With the mass production and consumption of polyester, waste such as polyester fiber and polyester packaging film is continuously generated. The waste polyester has strong chemical inertness, and is not easily degraded by air or microorganisms in a short time to cause white pollution. The recycling of the waste polyester materials not only protects the environment, but also is an important content of resource utilization in recycling economy.
Conventional polyester recycling techniques mainly include physical and chemical processes. The physical recycling technology usually adopts a mechanical crushing or re-melting and granulating mode to recycle the plastics.
Chemical recovery techniques typically employ chemical methods to degrade plastics into oligomers or monomers. The depolymerized product can partially replace the raw material for material production, and can be doped into new raw material to prepare new plastic material again. The reclaimed materials in this way can generally be added only in a low proportion, and once a certain addition amount is exceeded, the performance of the prepared material can be seriously affected. The monomer obtained by degradation can be used for obtaining high-purity basic raw materials again through a separation and purification technology, but the recovery mode usually has high requirements on temperature, pressure, reaction time and the like, and even supercritical conditions are required, the mixture obtained by degradation can be recycled only through a complicated purification and separation process, and the separation and purification difficulty is high and the cost is high.
Another polyester chemical recovery scheme is to depolymerize waste polyester by using dihydric alcohol, introduce dibasic acid, and perform polycondensation reaction under polymerization conditions to prepare copolyester. Patent specification CN107652423A discloses a method for preparing regenerated low-melting-point polyester by waste polyester alcoholysis, which comprises the following steps: 1) Pretreating waste polyester; 2) Alcoholysis of waste polyester; 3) Regulating and controlling the quality of the esterified product, and adding one or more comonomers of isophthalic acid, 1,4 cyclohexane dimethanol and neopentyl glycol; 4) Preparing polycondensation and slices; the final regenerated low-melting point polyester has intrinsic viscosity of 0.60-0.70 dl/g, melting point of 100-180 deg.c, diglycol content of 3.0 +/-0.3% and chroma b value less than 6. The patent specification with publication number CN105778066A discloses a low-melting-point copolyester and a preparation method thereof, which are synthesized by reacting polyester, at least one dibasic acid and at least one dihydric alcohol at room temperature to 300 ℃ in the presence of a catalyst in an environment; the polyester can be virgin polyester or recycled polyester; the low-melting-point polyester synthesized by the method has good co-adhesion and easy crystallization, and can be used for the fields of manufacturing bonding fibers, hot melt adhesives, color master batch carriers and the like. The former adopts the fractional method, namely the mode of alcoholysis first, then esterification and finally polycondensation to complete the conversion of the waste polyester to the copolyester, the latter adopts the one-pot method, the alcoholysis and the esterification are carried out synchronously, and the mode of polycondensation finally completes the conversion of the waste polyester to the copolyester. Particularly, the waste polyester raw materials have complex sources and poor batch stability, the components of the raw material polyester auxiliary agent are complex and unfixed, and if the auxiliary agents such as a catalyst and the like are introduced in the subsequent chemical recovery process, the color reaction among the auxiliary agents is easily caused, so that the appearance stability of the final product is poor.
Disclosure of Invention
Aiming at the technical problems and the defects in the field, the invention provides a method for preparing high-performance high-valued copolyester, which upgrades the general polyester raw material into the high-performance high-valued copolyester, and is particularly suitable for the field of preparing high-performance high-valued recycled polyester from recycled polyester.
The specific technical scheme is as follows:
a method for preparing high-performance high-valued copolyester is characterized by comprising the following steps: mixing polyester polyol and polyester raw materials, reacting for 0.5-12h at 190-280 ℃ under the condition of stirring, preferably reacting for 0.5-2h at 220-250 ℃, completing the melting and depolymerization of the polyester raw materials, continuously stirring and vacuumizing, controlling the temperature to be 180-300 ℃, preferably 200-280 ℃, the vacuum degree to be 1-500Pa, preferably 1-100Pa, and the reaction time to be 0.5-12h, preferably 0.5-3h, and polymerizing to obtain the high-performance high-valued copolyester.
The polyester polyol raw material has low molecular weight and low synthesis difficulty, can be prepared under the condition of no catalyst, has low alkyd ratio, does not need to feed a large amount of redundant dihydric alcohol raw material, has short reaction time and low side reaction degree, and does not need to extract a large amount of dihydric alcohol from a system to improve the molecular weight.
According to the invention, polyester polyol raw materials with corresponding structures are firstly synthesized according to the structural requirements of the copolyester, and are adopted to replace small molecular raw materials to react with the polyester, so that the reaction can be carried out at high temperature because the boiling point of the raw materials is not limited any more, and the reaction can be carried out at high temperature, so that the high-performance high-valued copolyester can be prepared in a short time even under the condition of no catalyst.
The invention starts from polyester polyol and polyester raw materials, and can directly prepare the high-performance high-valued copolyester product under the conditions of not replacing a reaction device, not adding extra dibasic acid and only changing reaction conditions.
In a preferred embodiment, the molecular weight of the polyester polyol is 400 to 10000.
Further preferably, the polyester polyol has a molecular weight of 1000 to 4000.
The polyester polyol is prepared by feeding an alcohol component raw material consisting of dihydric alcohol and an acid component raw material consisting of dibasic acid or dibasic acid anhydride or an ester compound of the dibasic acid according to a designed alcohol-acid ratio, performing esterification or ester exchange reaction, and then performing reduced pressure polycondensation reaction.
The alcohol component raw material and the acid component raw material of the polyester polyol used in the method of the invention can be selected according to the structure of the final high-performance high-valued copolyester product.
For example:
the raw material of the alcohol component of the polyester polyol can be one or more of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 3-butanediol, neopentyl glycol, 1, 6-hexanediol, nonanediol, decanediol, diethylene glycol, triethylene glycol, isosorbide, 1, 4-cyclohexanedimethanol, 2-methyl-1, 3-propanediol, ethylbutylpropanediol, trimethylpentanediol, polyethylene glycol with a molecular weight range of 200-4000, and polytetrahydrofuran ether glycol with a molecular weight range of 200-4000, wherein the 1, 4-cyclohexanedimethanol can be cis-form or trans-form or a cis/trans-form mixture.
The acid component raw material of the polyester polyol can be one or more of succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, 1, 4-cyclohexanedicarboxylic acid or anhydride or ester compounds thereof.
The polyester raw material can be one or more of polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT) and polybutylene terephthalate (PBT).
The polyester raw material can be one or more of raw polyester material, reclaimed polyester material and reclaimed polyester material.
The molar ratio of the acid component in the polyester polyol is not more than 90 percent based on the sum of the acid component in the polyester polyol and the amount of the terephthalic acid in the polyester raw material.
The molar ratio of the total components of the small molecule dihydric alcohol to the total components of the dibasic acid in the conventional method for preparing the copolyester is usually more than 2. By adopting the method, the total dosage proportion of the micromolecular dihydric alcohol is obviously smaller than that of the micromolecular dihydric alcohol in the traditional method. The molar ratio of the total components of dibasic acid in said polyester polyol and said polyester feedstock to the total components of dibasic acid in said polyester polyol and said polyester feedstock is from 1 to 1.7.
In a preferred embodiment, in the method for preparing high-performance high-valued copolyester, the polyester raw material is polybutylene terephthalate (PBT) reclaimed material and/or polyethylene terephthalate (PET) reclaimed material, the reaction temperature in the melting and depolymerization processes of the polyester raw material is 220-250 ℃, the reaction time is 0.5-2h, the reaction temperature in the polymerization process for obtaining the high-performance high-valued copolyester is 200-280 ℃, the vacuum degree is 1-100Pa, and the reaction time is 0.5-3h;
the molecular weight of the polyester polyol is 500-4000, the alcohol component raw material is ethylene glycol and/or 1, 4-butanediol, the acid component raw material is one or more of 1, 4-succinic acid, 1, 6-adipic acid or anhydride or ester compounds thereof;
the molar ratio of the acid component raw material in the polyester polyol is 10-80% based on the sum of the amounts of the acid component raw material in the polyester polyol and the terephthalic acid in the polyester raw material.
In a preferred embodiment, in the method for preparing high-performance high-valued copolyester, the polyester raw material is polyethylene terephthalate (PET) reclaimed material, the reaction temperature of the melting and depolymerization processes of the polyester raw material is 230-250 ℃, the reaction time is 0.5-2h, the reaction temperature of the polymerization process for obtaining the high-performance high-valued copolyester is 220-280 ℃, the vacuum degree is 1-100Pa, and the reaction time is 0.5-3h;
the molecular weight of the polyester polyol is 500-4000, the alcohol component raw material is 1, 4-butanediol, and the acid component raw material is one or more of terephthalic acid or ester compounds thereof;
the molar ratio of the acid component raw material in the polyester polyol is 10-90% based on the sum of the amounts of the acid component raw material in the polyester polyol and the terephthalic acid in the polyester raw material.
In a preferred embodiment, in the method for preparing the high-performance high-valued copolyester, the polyester raw material is polytrimethylene terephthalate (PTT), the reaction temperature in the processes of melting and depolymerization of the polyester raw material is 220-250 ℃, the reaction time is 0.5-2h, the reaction temperature in the process of obtaining the high-performance high-valued copolyester by polymerization is 200-280 ℃, the vacuum degree is 1-100Pa, and the reaction time is 0.5-3h;
the molecular weight of the polyester polyol is 500-4000, the alcohol component raw material is 1, 3-propylene glycol, and the acid component raw material is one or more of 1, 4-succinic acid, 1, 6-adipic acid or anhydride thereof or ester compounds thereof;
the molar ratio of the acid component raw material in the polyester polyol is 10-80% based on the sum of the amounts of the acid component raw material in the polyester polyol and the terephthalic acid in the polyester raw material.
In a preferred embodiment, in the method for preparing high-performance high-valued copolyester, the polyester raw material is polyethylene terephthalate (PET) reclaimed material, the reaction temperature of the melting and depolymerization processes of the polyester raw material is 230-250 ℃, the reaction time is 0.5-2h, the reaction temperature of the polymerization process for obtaining the high-performance high-valued copolyester is 240-280 ℃, the vacuum degree is 1-50Pa, and the reaction time is 0.5-3h;
the molecular weight of the polyester polyol is 500-4000, the alcohol component raw material is 1, 4-cyclohexanedimethanol, and the acid component raw material is one or more of terephthalic acid or ester compounds thereof;
the molar ratio of the acid component raw material in the polyester polyol is 10-90% based on the sum of the amounts of the acid component raw material in the polyester polyol and the terephthalic acid in the polyester raw material.
To increase the reaction rate, a catalyst may be used during the reaction. Polyesterification catalysts which may be used include tetrabutyl titanate, tetraisopropyl titanate, stannous octoate, dibutyltin dilaurate, monobutyltin oxide, zinc acetate, manganese acetate, antimony trioxide, antimony glycolate, antimony acetate, rare earth catalysts, used alone or in combination, but preferably no catalyst is added during the reaction.
Many different types of additives may also be added during the reaction, including antioxidants, nucleating agents, flame retardants, antistatic agents, etc., depending on the properties desired in the finished product.
The antioxidant can be selected from hindered phenol antioxidants, thioester antioxidants and phosphite antioxidants, and can be specifically selected from one or more of triphenyl phosphate, tricresyl phosphate, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl), isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, dioctadecyl pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite, tris [2, 4-di-tert-butylphenyl ] phosphite and N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, and the addition amount can be 0-1 percent of the total mass of the raw materials.
The nucleating agent can be selected from one or more of talcum powder, calcium carbonate, sodium benzoate, sarin resin, bluggeman P250 and Bluggeman P252, and the addition amount can be 0-10% of the total mass of the raw materials.
The flame retardant can be selected from one or more of decabromodiphenylethane, brominated polystyrene, brominated epoxy resin, aluminum hydroxide, magnesium hydroxide, montmorillonite and modified flame retardant thereof, antimony trioxide, triphenyl phosphate, tricresyl phosphate, triethyl phosphate, red phosphorus, ammonium polyphosphate and modified flame retardant thereof, aluminum hypophosphite and modified flame retardant thereof, melamine and modified flame retardant thereof, and polyphosphazene compound, and the addition amount can be 0-20% of the total mass of the raw materials.
The antistatic agent can be selected from one or more of carbon nano tube, graphene, quaternary ammonium salt, imidazolium salt, conductive carbon black and the like, and the addition amount of the antistatic agent can be 0-10% of the total mass of the raw materials.
Compared with the prior art, the invention has the following beneficial effects:
1. the polyester polyol raw material adopted by the invention has low molecular weight, low synthesis difficulty, short reaction time and low side reaction degree, and can be carried out under the condition of no catalyst. According to the invention, polyester polyol raw materials with corresponding structures are synthesized according to the structural requirements of the copolyester, and the polyester polyol raw materials are adopted to replace micromolecular raw materials to react with general polyester at high temperature, so that the polyester is rapidly melted and rapidly polymerized in a short time, and the high-performance high-valued copolyester is efficiently prepared. On one hand, reintroduction of the catalyst is reduced as much as possible, and batch stability is improved; on the other hand, the using amount of the dihydric alcohol component is greatly reduced, and a large amount of redundant dihydric alcohol component is not required to be removed in the polycondensation stage, so that the generation and the discharge of waste gas and waste liquid can be greatly reduced, byproducts are few, the production energy consumption is effectively reduced, the production time is shortened, the production cost is favorably reduced, and the call for energy conservation and emission reduction is responded.
2. For dihydric alcohol and dibasic acid monomers which are unstable at high temperature, such as butanediol, succinic acid and the like, the process method provided by the invention can effectively avoid side reactions of isomerization, decomposition, oxidation and the like of the raw materials, and effectively avoid raw material loss and byproduct generation.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
Preparing polyester polyol from 1, 4-Butanediol (BDO) and 1, 4-Succinic Acid (SA) according to a molar ratio BDO: SA =12, wherein the molecular weight of the polyol is 1984, mixing 541kg of polyester polyol with 440kg of polybutylene terephthalate (PBT) reclaimed material, reacting for 1.5h at 220 ℃ under the stirring condition, completing the melting and depolymerization of the polyester raw material, continuously stirring and vacuumizing, controlling the temperature to be 240 ℃, the vacuum degree to be 20Pa and the reaction time to be 2h, and polymerizing to obtain the high-performance high-valued PBST copolyester.
The copolyester PBST has excellent ductility and biodegradability, the tensile strength is 16MPa, the elongation at break is 700%, and the copolyester PBST is finally degraded into carbon dioxide and water under the composting condition.
Example 2
Preparing polyester polyol from 1, 4-butanediol and 1, 6-Adipic Acid (AA) according to a molar ratio BDO: AA =11, mixing 628kg of polyester polyol with 440kg of polybutylene terephthalate (PBT) reclaimed material, reacting for 1.5h at 220 ℃ under the stirring condition, completing the melting and depolymerization of the polyester raw material, continuously stirring and vacuumizing, controlling the temperature to be 240 ℃, the vacuum degree to be 50Pa and the reaction time to be 2h, and polymerizing to obtain the high-performance high-valued copolyester PBAT.
The copolyester PBAT has excellent ductility and biodegradability, tensile strength of 25MPa and elongation at break of 500 percent, and is finally degraded into carbon dioxide and water under the composting condition.
Example 3
Preparing polyester polyol from 1, 4-butanediol, 1, 4-succinic acid and 1, 6-adipic acid according to a molar ratio BDO: SA: AA = 11.
The copolyester PBAST has excellent ductility and biodegradability, the tensile strength is 20MPa, the elongation at break is 580 percent, and the copolyester PBAST is finally degraded into carbon dioxide and water under the composting condition.
Example 4
Preparing polyester polyol and polyol molecular weight 1936 from ethylene glycol and 1, 4-succinic acid according to a molar ratio EG: SA =14, mixing 300kg of polyester polyol and 576kg of polyethylene terephthalate (PET) reclaimed material, reacting for 1h at 230 ℃ under the stirring condition, completing the melting and depolymerization of polyester raw materials, continuously stirring and vacuumizing, controlling the temperature to be 250 ℃, the vacuum degree to be 50Pa, and reacting for 1h to obtain the high-performance high-valued copolyester PEST through polymerization.
The copolyester PEST has excellent ductility, 18MPa of tensile strength and 560 percent of elongation at break.
Example 5
Preparing polyester polyol by using ethylene glycol and 1, 6-adipic acid according to a molar ratio EG: AA =12 and a polyol molecular weight 1956, mixing 355kg of polyester polyol and 576kg of polyethylene terephthalate PET reclaimed material, reacting for 1h at 230 ℃ under the stirring condition, completing the melting and depolymerization of the polyester raw material, continuously stirring and vacuumizing, controlling the temperature to be 250 ℃, the vacuum degree to be 20Pa, and reacting for 1h to obtain the high-performance high-valued copolyester PEAT through polymerization.
The copolyester PEAT has excellent ductility and tensile property, the tensile strength is 26MPa, and the elongation at break is 860 percent.
Example 6
Preparing polyester polyol from ethylene glycol, 1, 4-succinic acid and 1, 6-adipic acid according to a molar ratio EG: SA: AA = 13.
The copolyester PEAST has excellent ductility and tensile property, tensile strength of 25MPa and elongation at break of 900 percent.
Example 7
Preparing polyester polyol from 1, 4-butanediol and 1, 4-succinic acid according to a molar ratio BDO: SA =12, wherein the molecular weight of the polyol is 1984, 541kg of polyester polyol and 384kg of polyethylene terephthalate (PET) reclaimed material are mixed and reacted for 1.5h at 220 ℃ under the stirring condition, the melting and depolymerization of the polyester raw material are completed, the stirring and the vacuumizing are continued, the temperature is controlled to be 240 ℃, the vacuum degree is 20Pa, the reaction time is 2h, and the high-performance high-valued copolyester PEBST is obtained through polymerization.
The copolyester PEBST has excellent ductility and biodegradability, the tensile strength is 17MPa, the elongation at break is 610%, and the copolyester PEBST is finally degraded into carbon dioxide and water under the composting condition.
Example 8
Preparing polyester polyol by using ethylene glycol and 1, 6-adipic acid according to a molar ratio EG: AA = 12.
The copolyester PEBAT has excellent ductility and tensile property, tensile strength of 25MPa and breaking elongation of 680 percent.
Example 9
Preparing polyester polyol and 2072 polyol by using 1, 4-butanediol and dimethyl terephthalate according to a molar ratio BDO: DMT = 10.
The copolyester PEBT has excellent toughness and high temperature resistance, the heat distortion temperature is 68 ℃, the impact strength is 450J/cm, and the tensile strength is 40MPa.
Example 10
Preparing polyester polyol from 1, 3-propanediol and 1, 4-succinic acid according to a molar ratio of PDO: SA =13, wherein the molecular weight of the polyol is 1974, mixing 330kg of the polyester polyol with 618kg of polytrimethylene terephthalate (PTT) reclaimed material, reacting for 0.5h at 220 ℃ under the stirring condition, completing the melting and depolymerization of the polyester raw material, continuously stirring and vacuumizing, controlling the temperature to be 200 ℃, the vacuum degree to be 100Pa and the reaction time to be 3h, and polymerizing to obtain the high-performance high-valued copolyester PPST.
The copolyester PPST has excellent tensile property and tensile strength of 20MPa.
Example 11
Preparing polyester polyol from 1, 3-propylene glycol and 1, 6-adipic acid according to a molar ratio PDO: AA =11, wherein the molecular weight of the polyol is 1939, mixing 390kg of polyester polyol with 618kg of polytrimethylene terephthalate (PTT) reclaimed material, reacting for 0.5h at 220 ℃ under the stirring condition, completing the melting and depolymerization of the polyester raw material, continuously stirring and vacuumizing, controlling the temperature to be 240 ℃, the vacuum degree to be 100Pa and the reaction time to be 1h, and polymerizing to obtain the high-performance high-valued copolyester PPAT.
The copolyester PPAT has excellent tensile property and 21MPa of tensile strength.
Example 12
Preparing polyester polyol and polyol molecular weight 2065 from 1, 4-cyclohexanedimethanol and dimethyl terephthalate according to a molar ratio CHDM: DMT =8, mixing 885kg of polyester polyol and 384kg of polyethylene terephthalate PET reclaimed material, reacting for 0.5h at 250 ℃ under the stirring condition, completing the melting and depolymerization of the polyester raw material, continuously stirring and vacuumizing, controlling the temperature to be 280 ℃, the vacuum degree to be 1Pa and the reaction time to be 3h, and polymerizing to obtain the high-performance high-valued copolyester PCTG.
The copolyester PCTG has excellent toughness and high temperature resistance, the heat distortion temperature is 80 ℃, the impact strength is 480J/cm, and the tensile strength is 40MPa.
Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention defined by the appended claims.
Claims (10)
1. A method for preparing high-performance high-valued copolyester is characterized by comprising the following steps: mixing polyester polyol and polyester raw materials, reacting for 0.5-12h at 190-280 ℃ under the stirring condition, preferably reacting for 0.5-2h at 220-250 ℃, completing the melting and depolymerization of the polyester raw materials, continuously stirring and vacuumizing, controlling the temperature to be 180-300 ℃, preferably 200-280 ℃, the vacuum degree to be 1-500Pa, preferably 1-100Pa, and the reaction time to be 0.5-12h, preferably 0.5-3h, and polymerizing to obtain the high-performance high-valued copolyester.
2. The method according to claim 1, wherein the polyester polyol has a molecular weight of 400 to 10000, preferably 1000 to 4000, and is prepared by feeding an alcohol component raw material consisting of a diol and an acid component raw material consisting of a dibasic acid or a dibasic acid anhydride or an ester compound of a dibasic acid in a designed alkyd ratio, performing esterification or transesterification, and then performing polycondensation under reduced pressure.
3. The method according to claim 1, wherein the polyester raw material is one or more of polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and polybutylene terephthalate (PBT).
4. The method of claim 1 or 3, wherein the polyester raw material is one or more of raw polyester material, recycled polyester material and recycled polyester material.
5. The process according to claim 1, wherein the molar ratio of the acid component in the polyester polyol is not more than 90% based on the sum of the acid component in the polyester polyol and the amount of terephthalic acid in the polyester starting material.
6. The process of claim 1, wherein the molar ratio of the total components of the dibasic acid in the polyester polyol and the polyester feedstock to the total components of the dibasic acid in the polyester polyol and the polyester feedstock is from 1 to 1.7.
7. The method according to claim 1, wherein the polyester raw material is polybutylene terephthalate (PBT) reclaimed material and/or polyethylene terephthalate (PET) reclaimed material, the reaction temperature of the melting and depolymerization processes of the polyester raw material is 220-250 ℃, the reaction time is 0.5-2h, the reaction temperature of the polymerization process for obtaining the high-performance high-valued copolyester is 200-280 ℃, the vacuum degree is 1-100Pa, and the reaction time is 0.5-3h;
the molecular weight of the polyester polyol is 500-4000, the alcohol component raw material is ethylene glycol and/or 1, 4-butanediol, the acid component raw material is one or more of 1, 4-succinic acid, 1, 6-adipic acid or anhydride or ester compounds thereof;
the molar ratio of the acid component raw material in the polyester polyol is 10-80% based on the sum of the amounts of the acid component raw material in the polyester polyol and the terephthalic acid in the polyester raw material.
8. The method according to claim 1, wherein the polyester raw material is polyethylene terephthalate (PET) reclaimed material, the reaction temperature of the polyester raw material in the melting and depolymerization processes is 230-250 ℃, the reaction time is 0.5-2h, the reaction temperature of the polymerization process for obtaining the high-performance high-valued copolyester is 220-280 ℃, the vacuum degree is 1-100Pa, and the reaction time is 0.5-3h;
the molecular weight of the polyester polyol is 500-4000, the alcohol component raw material is 1, 4-butanediol, and the acid component raw material is one or more of terephthalic acid or ester compounds thereof;
the molar ratio of the acid component raw material in the polyester polyol is 10-90% based on the sum of the amounts of the acid component raw material in the polyester polyol and the terephthalic acid in the polyester raw material.
9. The method according to claim 1, wherein the polyester raw material is polytrimethylene terephthalate (PTT), the reaction temperature in the melting and depolymerization processes of the polyester raw material is 220-250 ℃, the reaction time is 0.5-2h, the reaction temperature in the polymerization process for obtaining the high-performance high-valued copolyester is 200-280 ℃, the vacuum degree is 1-100Pa, and the reaction time is 0.5-3h;
the molecular weight of the polyester polyol is 500-4000, the alcohol component raw material is 1, 3-propylene glycol, the acid component raw material is one or more of 1, 4-succinic acid, 1, 6-adipic acid or anhydride thereof or ester compounds thereof;
the molar ratio of the acid component raw material in the polyester polyol is 10-80% based on the sum of the amounts of the acid component raw material in the polyester polyol and the terephthalic acid in the polyester raw material.
10. The method according to claim 1, wherein the polyester raw material is polyethylene terephthalate (PET) recycled material, the reaction temperature of the polyester raw material in the melting and depolymerization processes is 230-250 ℃, the reaction time is 0.5-2h, the reaction temperature of the high-performance high-valued copolyester obtained by polymerization is 240-280 ℃, the vacuum degree is 1-50Pa, and the reaction time is 0.5-3h;
the molecular weight of the polyester polyol is 500-4000, the alcohol component raw material is 1, 4-cyclohexanedimethanol, and the acid component raw material is one or more of terephthalic acid or ester compounds thereof;
the molar ratio of the acid component raw material in the polyester polyol is 10-90% based on the sum of the amounts of the acid component raw material in the polyester polyol and the terephthalic acid in the polyester raw material.
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| US20220348715A1 (en) * | 2019-10-25 | 2022-11-03 | Eastman Chemical Company | Copolyesters produced from recycled copolyesters |
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